CN111393869A - Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof - Google Patents
Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof Download PDFInfo
- Publication number
- CN111393869A CN111393869A CN202010259661.1A CN202010259661A CN111393869A CN 111393869 A CN111393869 A CN 111393869A CN 202010259661 A CN202010259661 A CN 202010259661A CN 111393869 A CN111393869 A CN 111393869A
- Authority
- CN
- China
- Prior art keywords
- fluorescent dye
- compound
- reaction
- phenylethynylnaphthalene
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a fluorescent dye containing phenylethynyl naphthalene, a preparation method and application thereof, wherein the chemical structural formula of the fluorescent dye containing phenylethynyl naphthalene is as follows:the fluorescent dye has good thermal stability, strong tinting strength, good light resistance, weather resistance and chemical stability, the fluorescent dye has high synthesis cost, expensive raw materials and complex preparation process, and the fluorescent dye can improve the problems, and can be industrially produced by simple process flow and cheap and easily obtained raw materials.
Description
Technical Field
The invention relates to a fluorescent dye containing phenylethynyl naphthalene and an organic synthetic intermediate, a preparation method and application research thereof.
Background
Fluorescent pigments have excellent dyeing performance in the coloring of plastic articles, sols, paper materials, colorants, dyes, paints, coatings, fiber products, textiles, and the like. Under natural conditions, even under light conditions of dawn, dusk, frost and fog weather, projection and the like, the visibility of the fluorescent luster is much better than the color of the traditional coloring agent. The fluorescent dye has high intensity, various colors and good fluorescence effect, and the characteristics of the fluorescent dye have wider commercial interest and obtain wider commercial application. Conventional fluorescent dyes are sensitive to pH changes, have a lower fluorescence intensity than the corresponding dye of the approximate wavelength, and have a small tolerance range, whereas fluorescent dyes containing phenylethynylnaphthalene are improved in this respect.
The invention discloses a fluorescent dye containing phenylethynyl naphthalene, belonging to a fluorescein dye, which is a compound with more benzene rings and a conjugated system, wherein a fused ring compound generated by a one-pot method can be used as an organic reaction intermediate, the compound contains a single acetylene bond which can be further cyclized with other compounds containing unsaturated bonds, the substrate has drug resistance, can be used as an excellent intermediate in the synthesis of natural products, medicines and design materials, is an excellent building block of a plurality of natural products and medicines, and is an important intermediate for synthesizing medicines.
Disclosure of Invention
The invention provides a novel method for synthesizing a dye or a drug intermediate containing phenylethynyl naphthalene, which has the advantages of simple reaction, better selectivity, stable reaction system and higher yield, and realizes a novel process for preparing a target compound by catalyzing a catalyst in multiple steps.
The technical scheme of the invention is as follows:
a fluorescent dye containing phenylethynyl naphthalene and an organic synthesis intermediate, wherein the chemical structural formula of the compound is as follows:
wherein, the substituent R1Is H, CmH2m+1、CmH2m-1、 CmH2m-3Isoalkyl or OCH3、NH2Any one of the electron donating groups; r2Is F, Cl, Br, I, NO2、OCOR、CHO、CH2OR、CO2R, and the like electron-withdrawing groups; r3Is CH3、 CmH2m+1Any one of the alkyl groups such as alkyl, alkoxy,the synthesis method comprises the following steps of preparing an alkynol compound by taking an aromatic ketone compound and an aromatic acetylene compound as raw materials, reacting the alkynol compound with a diacid diester under the catalysis of L ewis acid through a one-pot method to form a Diels-Alder reaction, and synthesizing the compound, wherein m is an integer between 1 and 20, and the positions, the number and the conjugated positions of the substituent groups are not fixed:
the method comprises the following steps:
the method comprises the following steps of firstly, adding a compound 2 and THF into a reaction bottle under the protection of nitrogen, cooling to-25-10 ℃ after stirring, dropwise adding n-Bu L i, effectively reducing the reaction concentration of butyl lithium in a dropwise adding mode, enabling the concentration of the butyl lithium in a system to be more uniform, enabling the reaction to be more stable and mild, reducing the reaction disadvantage caused by the sharp temperature change of the system due to instantaneous violent reaction, and facilitating the formation of an intermediate product, reacting for a period of time (preferably, the reaction time is 0.5-1h) at the temperature, continuing the reaction for a period of time (preferably, the reaction time is 0.5-1h) at room temperature, cooling to-25-10 ℃ again, dropwise adding the compound 1, continuing the reaction for a period of time (preferably, the reaction time is 2-4h), and facilitating the reaction to proceed mildly and forwardly after repeated cooling treatment reactions, so that the yield of the intermediate is increased, and the conversion rate is increased.
And step two, detecting a reaction end point of the step one by using a T L C point plate (detecting by using a T L C point plate, detecting every 1h by using the T L C point plate, when the plate is clicked, a point of the raw material compound 1 disappears, a new point is generated above or below the raw material point, stopping the reaction, and reacting for 3-4h), extracting a reaction solution by using a mixed solution of ethyl acetate and water to ensure that the obtained product is fully dissolved in the ethyl acetate (the product has good solubility in the ethyl acetate), dissolving a solvent in water, removing other organic impurities by the operation to achieve the aim of coarse purification, performing rotary evaporation and column chromatography separation on the obtained organic layer to obtain a product 3, wherein the compound obtained by series of operations is more pure, and the byproducts generated by the latter reaction are less when the product is put into the next reaction.
Step three, mixing the product 3, the compound 4 and SnCl2Mixing with toluene, stirring, carrying out reflux reaction at 110-120 ℃ for a period of time (preferably 10-17 h), detecting a reaction end point by using a T L C point plate (detecting by using a T L C point plate, detecting that a fluorescent point is generated by using the point plate after reaction for 15min, and detecting that the reaction is finished when 3 points of raw materials disappear by using the point plate), carrying out column chromatography separation, and collecting a product 5, namely a target compound, wherein the product is a high yield which is obtained at the preferred temperature of 110 ℃, so that the compound can still exist stably under the heating condition, and the yield can still be kept constant after the heating temperature is increased, so that the compound is stable in structure and not influenced by high temperature, and the compound is not obviously resistant to heat, which is an advantage that the compound can be applied.
In the step one, the feeding molar ratio of the compound 1, the compound 2 and the catalyst n-Bu L i is 0.9-2.0: 1.0-2.5: 1.0-1.5, and the feeding molar ratio of the compound 1, the compound 2 and the catalyst n-Bu L i is further preferably 0.9: 1.5: 1.1.
The dissolving temperature of the first step is 25 ℃; the reaction temperature was-25 ℃.
In the second step, the volume ratio of water to ethyl acetate is 1: 1.5-3.
Product 3, compound 4 and SnCl in the step three2In a molar ratio of 0.1 to 1.5: 1.5-2.5: 0.1-3.0. The product 3, the compound 4 and SnCl in the step three in the step (3)2In a molar ratio of 0.1 to 1.5: 1.5-2.5:0.1-3.0. Preferably, the compound 3, the compound 4 and the catalyst SnCl2The feeding molar ratio of (A) to (B) is 0.1: 2.0: 0.1.
the dissolving temperature of the third step is 45 ℃; the reaction temperature was 110 ℃ and the solvent was toluene.
The fluorescent dye containing phenylethynylnaphthalene and the organic synthesis intermediate are applied to aspects of dye coloring, compound synthesis and the like.
The invention has the following beneficial effects:
1. the invention discloses a preparation route for synthesizing fluorescent dye containing phenylethynyl naphthalene and organic synthesis intermediate in a short time by one-pot method under the catalysis of Lewis acid for the first time. The method has the advantages of simple operation, few byproducts, high reaction speed, stable reaction at 110 ℃ or even higher temperature, no decomposition, no influence on the activity of the catalyst, simple post-reaction treatment and higher use value.
2. The invention prepares a new fluorescent dye containing phenylethynyl naphthalene and an organic synthesis intermediate, and the reaction environment is as follows: the reaction is carried out for a long time under the conditions of high temperature, strong acid and illumination, the reaction yield is high, the separation effect is good, and a novel preparation method with low preparation cost, simple operation and high reaction efficiency is provided.
3. The invention prepares a new fluorescent dye containing phenylethynyl naphthalene and an organic synthesis intermediate, in the reaction process, the reaction environment is not protected from light, oxygen is not isolated, the pH value is 1-2, the reaction temperature is at 110-130 ℃ for 17-24 h (the longest reaction time is 42h), the obtained product is still stable and not decomposed, a small amount of SnCl is selected2The strong acidic L ewis acid catalysts such as TsOH and the like have good catalytic effect in a short time, and the reaction conditions of experiments show that the fluorescent dye has the advantages of good tolerance, difficult influence of light, temperature and pH and the like.
Drawings
FIG. 1 is a hydrogen spectrum of the product of example 1.
FIG. 2 is a carbon spectrum of the product of example 1.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Instruments and reagents:
an SHZ-E type circulating water vacuum pump (Shanghai Rongya chemical instrument factory), a DZE-6120 type vacuum drying box (Shanghai Hengtian scientific instrument manufacturing company), a WRS-1A digital melting point instrument (Shanghai Soo photoelectricity technology limited company), an EB2005A electronic balance, a ZF-I type three-purpose ultraviolet analyzer, a DE-102J heat collection type constant temperature heating magnetic stirrer (Chengyi Huafa chemical instrument factory), a DFX-5L/30 low temperature constant temperature reaction bath (Wuchuan instrument factory of Wuxi city), a 2YZ-4A type rotary vane type vacuum oil pump (Yonghao vacuum equipment factory of Linhai city), toluene (AR), stannous chloride (AR), n-butyl lithium (AR), tetrahydrofuran (AR), Acetophenone (AR), phenylacetylene (AR), dimethyl butynoate (AR), distilled water (AR), petroleum ether (AR), ethyl Acetate (AR), and industrial nitrogen (AR).
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Instruments and reagents:
the melting point was measured by X4 type melting point apparatus (manufactured by Beijing third Optic instruments Co., Ltd.), and the thermometer was not corrected;1h NMR and13c NMR was measured using a Varian Mercury 400 model 400MHz NMR spectrometer or a Varian Mercury 600 model 600MHz NMR spectrometer using deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d)6) TMS as an internal standard, MS as a solvent, by Finnigan Trace mass spectrometer, elemental analysis by Vario E L III elemental analyzer, and reagents used as domestic (or imported) chemically pure or analytically pure solvent toluene are dried.
Example 1
A process for the preparation of dimethyl 4- (phenylvinyl) naphthalene-1,2-dicarboxylate comprising the following experimental steps:
under the protection of nitrogen, adding phenylacetylene 2(3.96m L, 36mmol, 1.5eq) and THF (120ml) into a 250m L Schlenk bottle, redistilling the THF before use, stirring for a few minutes, cooling to-25 ℃, dropwise adding n-Bu L i (11m L, 26.4mmol, 1.1eq) and reacting for 0.5h at the temperature, removing the reaction bottle, continuing to react for 0.5h at room temperature, wherein the reaction liquid is a light yellow liquid, cooling to-25 ℃, dropwise adding acetophenone 1(2.56m L, 22mmol, 0.9) and continuing to react for 3h, detecting by using a T L C point plate, detecting every 1h point plate, finding that the point of the raw acetophenone disappears, generating a new point below the point, after the reaction time is about 4h, extracting the reaction liquid by using 20m L of water and ethyl acetate 30m L, distilling an organic layer to obtain a dimethyl ester, performing column chromatography to obtain a dimethyl ester, separating, filtering a reaction liquid, collecting a reaction liquid, purifying a product, purifying by using a diphenyl alcohol column chromatography, separating a mixture, collecting a product, purifying a product, and purifying a product, wherein the product is obtained by using the product obtained by using the method comprises the steps of 2-2 m L, 2 m-3 m-2 m acetylene alcohol, 2m2(0.22g, 1mmol, 0.1eq) and toluene (20m L) were stirred and refluxed at 110 ℃ for 12h, detection was performed using a T L C dot plate, generation of a green fluorescent dot was observed after 10min of reaction, when the 3 dots of the raw material disappeared, the reaction was completed, the resulting mixture was separated by column chromatography, the product dot was collected, and the compound 4- (phenylethynyl) naphthalene-1, 2-dicarboxylic acid dimethyl ester 5 was obtained after rotary evaporation, with a yield of 0.76 g.
Hydrogen spectrum:
1H NMR(CDCl3,400MHz)(ppm)8.50(d,J=8.3Hz,1H),8.31(s,1H),7.90 (d,J=8.4Hz,1H),7.73(t,J=7.6Hz,1H),7.69–7.62(m,3H),7.46–7.39(m,3H), 4.09(s,3H),3.98(s,3H).
carbon spectrum:
13C NMR(101MHz,CDCl3)169.18,165.69,134.74,131.78,129.28, 129.22,128.92,128.52,128.19,126.57,124.40,122.69,96.08,86.23,52.99, 52.81.
GC-MS (ESI): m/z: calculated values: 344.3611, respectively; experimental values: 344.0000
Example 2
A method of preparing dimethyl 4- ((4-chlorophenylyl) ethyl) -7-methylnaphthalene-1, 2-dicarboxylate comprising the following experimental steps:
under the protection of nitrogen, 4-chloroacetylene 2(3.97m L, 36mmol, 1.5eq) and THF (120ml) are added into a 250m L Schlenk bottle, the THF is steamed again before use, after stirring for a few minutes, the temperature is reduced to-25 ℃, n-Bu L i (11m L, 26.4mmol, 1.1eq) is added dropwise, the reaction is carried out for 0.5h at the temperature, the reaction bottle is removed, the reaction is continued for 0.5h at room temperature, the temperature is reduced to-25 ℃, 4-methylacetophenone 1(2.94m L, 22mmol, 0.9eq) is added dropwise, the reaction is continued for 3h, the detection is carried out by using a T L C point plate, new points are generated after the disappearance of the point of the raw material 4-methylacetophenone is found every 1h, after the reaction time is about 3h, the reaction liquid is extracted by using 20m L and ethyl acetate 30m L, an organic layer is steamed, the obtained mixture is subjected to column chromatography, the obtained mixture is subjected to separation, a dimethyl chloride-4- (tolyl) -acetylene alcohol (2.54 g) is collected, and a reaction product is added, the reaction is obtained, the reaction is purified, the reaction is added, the reaction is carried out2(0.22g, 1mmol, 0.1eq) and toluene (20m L) were stirred and refluxed at 110 ℃ for 12h, detection was performed using a T L C dot plate, after 10min of reaction, generation of a fluorescent dot was observed on the dot plate, when 3 dots of the raw material disappeared, the reaction was completed, the resulting mixture was separated by column chromatography, and the product dot was collected and rotary distilled to obtain 4- ((4-chlorophenyl) ethynyl) -7-methylnaphthalene-1, 2-dicarboxylic acid dimethyl ester 5, the yield was 0.90 g.
Example 3
A method of preparing dimethyl 7-methoxy-4- ((4-nitrophenyl) ethyl) naphthalene-1,2-dicarboxylate comprising the following experimental steps:
under nitrogen protection, 4-nitrophenylacetylene 2(5.29g, 36mmol, 1.5eq), THF (120ml) was added to a 250m L Schlenk flask, which was allowed to redistill before use, stirred for a few minutes,cooling to-25 ℃, dropwise adding n-Bu L i (11m L, 26.4mmol, 1.1eq), reacting at the temperature for 0.5h, removing the reaction flask, continuing to react at room temperature for 0.5h, cooling to-25 ℃, adding 4-methoxyacetophenone 1(3.30g, 22mmol, 0.9eq), continuing to react for 3h, detecting by using a T L C point plate, finding new points after the points of the raw material 4-methoxyacetophenone disappear every 1h, after the reaction time is about 3h, extracting the reaction liquid by using 20m L of water and 30m L of ethyl acetate, carrying out rotary evaporation on an organic layer, separating the obtained mixture by using column chromatography, filtering and collecting a product 2- (4-methoxyphenyl) -4- (4-nitrophenyl) -3-alkyne-2-ol 3, taking a clean reaction flask, adding compound 3(0.59g, 2mmol, 1.0eq), dimethyl acetylenate 4(0.57g, Sn0.57 g), Sn0.9 mmol, Sn0.25 g, and Sn0.57 eq2(0.22g, 1mmol, 0.1eq) and toluene (20m L) are stirred, the reflux reaction is carried out for 12h at 110 ℃, the detection is carried out by using a T L C dot plate, after the reaction is carried out for 10min, a fluorescent dot is generated on the dot plate, after the reaction is finished when the 3 dots of the raw material disappear, the obtained mixture is separated by using column chromatography, the product dot is collected, and the 7-methoxy-4- ((4-nitrophenyl) ethynyl) naphthalene-1, 2-dicarboxylic acid dimethyl ester 5 is obtained after rotary evaporation, wherein the yield is 0.84 g.
Example 4
A method of preparing diethyl 7-methoxy-4- ((4-nitrophenyl) ethyl) naphthalene-1,2-dicarboxylate comprising the following experimental steps:
under the protection of nitrogen, 4-nitrophenylacetylene 2(5.29g, 36mmol, 1.5eq) and THF (120ml) are added into a 250m L Schlenk bottle, the THF is steamed again before use, after stirring for a few minutes, the temperature is reduced to-25 ℃, n-Bu L i (11m L, 26.4mmol, 1.1eq) is added dropwise and the reaction is carried out for 0.5h at the temperature, the reaction bottle is removed, the reaction is continued for 0.5h at room temperature, the temperature is reduced to-25 ℃, 4-methoxyacetophenone 1(3.30g, 22mmol, 0.9eq) is added and the reaction is continuedDetecting by using a T L C point plate for 3h, when the point of the raw material 3-chloroacetophenone disappears and a new point is generated every 1h, after the reaction is finished for about 3h, extracting the reaction liquid by using 20m L of water and 30m L of ethyl acetate, carrying out rotary evaporation on an organic layer, separating the obtained mixture by using column chromatography, filtering and collecting a product 2- (4-methoxyphenyl) -4- (4-nitrophenyl) -3-alkyne-2-alcohol 3, taking a clean reaction bottle, adding the compound 3(0.54g, 2mmol, 1.0eq), diethyl butynedioate 4(0.68g, 4mmol, 2.0eq), SnCl and the like2(0.22g, 1mmol, 0.1eq) and toluene (20m L) were stirred and reacted at 110 ℃ under reflux for 12h, detection was performed using a T L C dot plate, after 10min of reaction, generation of a fluorescent dot was observed on the dot plate, when the 3 dots of the starting material disappeared, the reaction was completed, the resulting mixture was separated by column chromatography, the product dots were collected, and the yield of diethyl 7-methoxy-4- ((4-nitrophenyl) ethynyl) naphthalene-1,2-dicarboxylate 5 was 0.84g after rotary evaporation.
The application of the fluorescent dye containing phenylethynyl naphthalene and the organic synthesis intermediate provided by the invention is as follows:
the fluorescent dye containing phenylethynylnaphthalene belongs to fluorescein dyes, is a compound with more benzene rings and a conjugated system, can be combined with a plurality of antibody proteins, has stable performance, is easy to show blue-green fluorescence in alkaline solution, and has great application potential in organic synthesis.
The invention provides a method for preparing anthracene fluorescent substance and dinaphthalene substance by taking phenylethynyl naphthalene as an organic synthesis intermediate:
wherein, the substituent R1Includes H, CmH2m+1、CmH2m-1、CmH2m-3Alkyl or OCH of3、NH2Any one ofElectron donating groups of (a); r2Including F, Cl, Br, I, NO2、OCOR、CHO、CH2OR、 CO2An electron withdrawing group of any one of R; r3、R4Including CH3、CmH2m+1Alkyl groups of (a); m is an integer of 1 to 20.
The specific synthesis method of the anthracene fluorescent substance is as follows:
adding compound 5(0.345g, 1mmol, 1eq), toluene (5ml) and 6(0.152g, 2mmol, 2eq) into a 25m L Schlenk bottle under the protection of nitrogen, stirring, refluxing at 110 ℃ for 2h, monitoring by using a T L C dot plate, detecting that a strong fluorescence spot is generated, after 5 dots of raw materials disappear, finishing the reaction, separating the obtained mixture by using column chromatography, collecting product dots, and performing rotary evaporation to obtain the anthracene compound 7 with the yield of 0.193 g.
The specific synthesis method of the binaphthyl fluorescent substance is as follows:
under the protection of nitrogen, adding compound 5(0.345g, 1mmol, 1eq), toluene (5ml) and 9(0.152g, 2mmol, 2eq) into a 25m L Schlenk bottle, starting stirring, reacting at room temperature (25 ℃) for 8h, monitoring by using a T L C dot plate, detecting that a fluorescent dot is generated, after 5 dots of raw materials disappear, finishing the reaction, separating the obtained mixture by using column chromatography, collecting product dots, and performing rotary evaporation to obtain the binaphthyl compound 8, wherein the yield is 0.315 g.
The fused ring compound of the phenylethynyl naphthalene generated by the one-pot method can be used as a reaction intermediate, the compound contains a single acetylene bond which can be further cyclized with other compounds containing unsaturated bonds, the substrate has tolerance, is an excellent building block of a plurality of natural products and chemicals, is an important intermediate for synthesizing organic matters, and the application of the intermediate needs further research and development so as to achieve better commercial value.
Claims (9)
1. The fluorescent dye containing phenylethynyl naphthalene is characterized in that the structural formula of the fluorescent dye is as follows:
2. The phenylethynylnaphthalene-containing fluorescent dye according to claim 1, wherein R is1、R2The substituent position and the conjugate position are not fixed.
4. The method for preparing a phenylethynylnaphthalene containing fluorescent dye according to any one of claims 1-3, comprising the following synthetic route:
step one, adding a compound 2 and THF into a reaction bottle under the protection of nitrogen, cooling to-25 to-10 ℃ after stirring, dropwise adding n-Bu L i, reacting at the temperature for a period of time, continuing to react at room temperature for a period of time, cooling to-25 to-10 ℃ again, dropwise adding a compound 1, and continuing to react for a period of time;
step two, detecting the reaction end point of the step one by using a T L C point plate, extracting the reaction solution by using a mixed solution of ethyl acetate and water, performing rotary evaporation and column chromatography separation, and collecting a product 3;
step three, mixing the product 3, the compound 4 and SnCl2Mixing with toluene, stirring, refluxing at 110-120 deg.C for a period of time, detecting the reaction end point with a T L C point plate, separating by column chromatography, and collecting the product 5, i.e. the target compound.
5. The method for preparing a fluorescent dye containing phenylethynylnaphthalene according to claim 4, wherein the molar ratio of compound 2, n-Bu L i and compound 1 in the first step is 1.0-2.5: 1.0-1.5: 0.8-2.0.
6. The method for preparing a fluorescent dye containing phenylethynylnaphthalene according to claim 4, wherein the volume ratio of water to ethyl acetate in the second step is 1: 1.5-3.
7. The method for preparing fluorescent dye containing phenylethynylnaphthalene according to claim 4, wherein the product 3, the compound 4 and SnCl are obtained in step three2In a molar ratio of 0.1 to 1.5: 1.5-2.5: 0.1-3.0.
8. Use of the phenylethynylnaphthalene containing fluorescent dye according to any one of claims 1-3 in the preparation of anthracene fluorescent substance.
9. Use of a fluorescent dye containing phenylethynylnaphthalene according to any one of claims 1 to 3 for the preparation of a dinaphthalene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010259661.1A CN111393869B (en) | 2020-04-03 | 2020-04-03 | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010259661.1A CN111393869B (en) | 2020-04-03 | 2020-04-03 | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111393869A true CN111393869A (en) | 2020-07-10 |
CN111393869B CN111393869B (en) | 2021-05-18 |
Family
ID=71427786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010259661.1A Active CN111393869B (en) | 2020-04-03 | 2020-04-03 | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111393869B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113372219A (en) * | 2021-05-17 | 2021-09-10 | 三峡大学 | Method for preparing ethynylnaphthalene derivative by [4+2] cyclization reaction with water as solvent |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106146359A (en) * | 2016-07-29 | 2016-11-23 | 江西师范大学 | The gentle efficient preparation method of α acyloxy acrylamide compound and the application in amide and Peptide systhesis thereof |
CN110272428A (en) * | 2018-03-16 | 2019-09-24 | 中国科学院大连化学物理研究所 | A kind of acid resistance role in fluorescent molecule switch that visible light is light-operated and its synthetic method |
-
2020
- 2020-04-03 CN CN202010259661.1A patent/CN111393869B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106146359A (en) * | 2016-07-29 | 2016-11-23 | 江西师范大学 | The gentle efficient preparation method of α acyloxy acrylamide compound and the application in amide and Peptide systhesis thereof |
CN110272428A (en) * | 2018-03-16 | 2019-09-24 | 中国科学院大连化学物理研究所 | A kind of acid resistance role in fluorescent molecule switch that visible light is light-operated and its synthetic method |
Non-Patent Citations (1)
Title |
---|
VALENTINA PIROVANO等: "Synthesis and photophysical properties of isocoumarin-based D-π-A systems", 《DYES AND PIGMENTS》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113372219A (en) * | 2021-05-17 | 2021-09-10 | 三峡大学 | Method for preparing ethynylnaphthalene derivative by [4+2] cyclization reaction with water as solvent |
Also Published As
Publication number | Publication date |
---|---|
CN111393869B (en) | 2021-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4652657A (en) | Chiral rhodium-diphosphine complexes | |
Jiao et al. | A coumarin-based chiral fluorescence sensor for the highly enantioselective recognition of phenylalaninol | |
CN111393869A (en) | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof | |
CN111171068B (en) | Preparation method of silicon spiro-compound | |
CN109651151B (en) | Polysubstituted phenanthrene derivative and preparation method thereof | |
Son et al. | Synthesis of planar chiral tricarbonylcyclopentadienylmanganese complexes using a Mn (CO) 3+ transfer reactionElectronic supplementary information (ESI) available: characterization of 2b, 2c, 4, 6, 7, 8 and 9, and a typical procedure for Pd-catalyzed allylic alkylation. See http://www. rsc. org/suppdata/cc/b1/b102693n | |
CN113387886B (en) | 2-aminodibenzo [ c, e ] azepine compound and synthetic method thereof | |
CN104628753B (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
CN110304982B (en) | Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof | |
CN111205261B (en) | Method for synthesizing naphthopyran-2-ketone compound | |
CN110105382B (en) | 1,1,2, 2-tetraborate ethylene and preparation method and application thereof | |
CN108794420B (en) | Bis-oxazoline ligand compound based on tetramethyl spiroindane skeleton, intermediate thereof, preparation method and application | |
CN113308131A (en) | Carboxyl modified near-infrared squaric acid dye and preparation method and application thereof | |
CN111233616A (en) | Pyrenyl [4] helicene and synthesis method and application thereof | |
CN109761917A (en) | Isolonglifolane ketone group -2- Aminopyrimidines boron trifluoride fluorescence probe and its synthetic method and application | |
CN109232169A (en) | A kind of polyaryl replaces fulvalene compound and its synthetic method | |
Gotov et al. | Novel Chiral 1-(ferrocenylalkyl)-(S)-prolinols and their application in enantioselective synthesis | |
CN105713003B (en) | π extends equal San Dan Za guans derivatives and its synthetic method | |
CN1817857A (en) | Production of 1,4-bis(O-styryl) | |
CN109265311B (en) | Phenyl fluorene derivative and preparation method and application thereof | |
Xi et al. | Copper-Catalyzed Enantioselective Radical Esterification of Propargylic C–H Bonds | |
CN115947714B (en) | Synthesis method of photochemical caching agent | |
CN113880870B (en) | Pyridine fluorine boron fluorescent dye compound and preparation method thereof | |
CN114685530B (en) | Aggregation-induced emission molecule based on isoquinoline and preparation method thereof | |
CN113912618A (en) | Dioxa [5] spiroalkene compound and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |